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In this paper, a novel mesoporous silica gel evenly doped by Prussian blue nanoparticles (PBMSG) was successfully synthesized by using N,N-dimethylamide as template with a large Barrett-Emmett-Teller (BET) surface area of 505m2/g and an average pore size of 2.9 nm. The static adsorption experiments showed that the equilibration time of PBMSG for Cs+ was about 30 min. The adsorption isotherm of PBMSG for Cs+ accorded with Langmuir model and the theoretical maximum adsorption capacity was 80.0 ± 2.9 mg/g. When the initial concentration of Cs+ was 1.00 mg/L, the adsorption partition coefficient Kd could reach 3.5 ×104 mL/g After adsorption, Cs+ could be eluted by dilute hydrochloric acid (pH 2) with an efficiency of 89.8％, while no K+, Fe3+, Fe2+was eluted. PBMSG exhibited good selectivity toward Cs+ and Rb+. In the presence of high concentration of K+, the selective adsorption of PBMSG could change the mass ratio of K+, Rb+ and Cs+ from 96.63:0.83:1.00–1.12:0.73:1.00. The separation of Cs+ and Rb+ from K+ with similar concentration (100 mg/g) was realized by column experiment. This indicated that PBMSG was suitable for rapid recovery of low concentration of rubidium and cesium from complex matrixes, such as wastewater and salt lake brine, etc.